Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/48—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
  • C08G75/23—Polyethersulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

• the invention relates to new aromatic polyethers, preferably polyphenylene ethers with pendant keto groups, and their use.
• Aromatic polyethers e.g. Polyphenylene oxide (PPO), polyether sulfones, polyether ketones, polyether amides are highly heat-resistant polymers. They are less sensitive to oxidation and flame retardant. Semi-crystalline polyarylene ethers, e.g. Polyetheretherketones (PEEK). are also resistant to chemicals and solvents.
• PPO Polyphenylene oxide
• PEEK Polyetheretherketones
• these polymers can be prepared by nucleophilic substitution reactions in dipolar aprotic solvents. To produce PPO by such reactions is not yet known.
• the polymers produced by nucleophilic substitution reactions no longer have a functional (reactive) group. They can be used for certain technical applications, e.g. hardly used as membrane materials for gas separation.
• New aromatic polyethers preferably with pendant keto groups, have been found which are accessible by nucleophilic substitution reactions.
• the invention relates to aromatic polyethers, preferably with pendant keto groups of the formula (I) in which Ar represents a C6-C30-aryl radical which is optionally substituted by C1-C4-alkyl, C6-C14-aryl, C7-C24-aralkyl and -alkaryl, Ph is optionally with -X-C1-C4-alkyl, -X-C1-C14-aryl, where X is oxygen (O) or sulfur (S) and n represents an integer from 3 to 250.
• Ar represents a C6-C30-aryl radical which is optionally substituted by C1-C4-alkyl, C6-C14-aryl, C7-C24-aralkyl and -alkaryl
• Ph is optionally with -X-C1-C4-alkyl, -X-C1-C14-aryl, where X is oxygen (O) or sulfur (S) and n represents an integer from 3 to 250.
• Ar is preferably a radical of the formula (Ia) in which X represents a chemical bond, an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group or a C3-C20 alkylene radical, preferably isopropylidene, R1 to R4 independently of one another for hydrogen, C1-C20 alkyl, preferably hydrogen, methyl, C6-C14 aryl or halogen such as Cl, Br is.
• n in formula (I) stands for an integer from 3 to 250, preferably 5 to 200, particularly preferably 5 to 150.
• the invention relates to a process (A) for producing the aromatic polyethers, preferably of the formula (I) in which Ar represents a C6-C30-aryl radical which is optionally substituted by C1-C4-alkyl, C6-C14-aryl, C7-C24-aralkyl and -alkaryl, Ph is optionally with -X-C1-C4-alkyl, -X-C1-C14-aryl, where X is oxygen (O) or sulfur (S) and n represents an integer from 3 to 250, characterized in that, in a manner known per se, dihalobenzophenones of the formula (II) in which Hal represents halogen such as fluorine (F), chlorine (Cl), preferably fluorine, Ph has the meaning given for formula (I), With Bistrialkylsilyl ethers of the formula (III) R53Si-O-Ar-O-SiR53 (III), in which R5 represents an optionally branched C
• the trimethylsilyl ethers of formula (III) are known and can e.g. produced in a known way by reacting bisphenols with hexamethyldisilazane and e.g. can be isolated by fractional distillation in vacuo or crystallization.
• Suitable diols for the preparation of the silyl ethers are, for example, hydroquinone, methylhydroquinone, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, 4,4'-dihydroxydiphenyl ether, bis (4-hydrophenyl) methane, 2,2- Bis (4-hydroxyphenyl) propane (bisphenol A), 1,6-, 1,7-, 2,6- and 2,7-naphthalenediol, phenophthalein, etc
• dihalogen compounds of the formula (II) are 2,6-difluorobenzophenone, 2,6-difluoro-4'-methoxybenzophenone, 2,6-difluoro-4'-methyl-benzophenone, 2,6-difluoro-4 '- ( 4-acetylyl-phenoxy) -benzophenone, 2,6-difluoro-4'-methylmercapto-benzophenone, etc They are known and can e.g. be produced by known methods.
• condensation reactions for the preparation of the new polyaryl ethers can be carried out by salts, e.g. Alkali salts such as alkali halides, e.g. CSF, catalyzed.
• salts e.g. Alkali salts such as alkali halides, e.g. CSF, catalyzed.
• Salts are preferably suitable as catalysts which dissociate into a soft cation and hard anion in the solvent used.
• the process according to the invention can be carried out with and without a diluent. It is preferably carried out without a diluent.
• the reaction is carried out at temperatures of 180 to 220 ° C. The temperature is gradually increased during the condensation. The final temperatures are between 280 and 320 ° C. At the end of the reaction, a vacuum (up to approx. 10 ⁇ 3 bar) is applied. Volatile trialkylsilyl halide is obtained as a by-product.
• the process can be carried out such that e.g. a 2,4- or 2,6-dihalobenzophenone is used with another activated dihaloaromatic in a mixture for the condensation.
• Dihalobenzophenones can be polycondensed with mixtures of several silylated bisphenols.
• the invention relates to a process (B) for the preparation of the aromatic polyethers of the formula (I) in which Ar represents a C6-C30-aryl radical which is optionally substituted by C1-C4-alkyl, C6-C14-aryl, C7-C24-aralkyl and -alkaryl, Ph is optionally with -X-C1-C4-alkyl, -X-C1-C14-aryl, where X is oxygen (O) or sulfur (S) and n represents an integer from 3 to 250, characterized in that, in a manner known per se, dihalobenzophenones of the formula (II) in which Hal represents halogen such as fluorine (F), chlorine (Cl), preferably fluorine, Ph has the meaning given for formula (I), with aromatic dihydroxy compounds of the formula (IV) HO-Ar-OH (IV), in which Ar has the meaning given for formula (I), in the presence of 1 to 1.3 equivalents of basic catalysts, based
• the reaction time is generally one to 50 hours, preferably 2 to 20 hours.
• dihalobenzophenones of the formula (II) are 2,6-difluorobenzophenone, 2,6-dichlorobenzophenone, 2,4-difluorobenzophenone, 2,4-dichlorobenzophenone, etc.
• dihydroxy compounds of the formula (IV) are hydroquinone, methylhydroquinone, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane ( Bisphenol A), 1,6-, 1,7-, 2,6-, 2,7-naphthalenediol, etc.
• solvents of the formula (V) are N-methylpyrrolidone, N-methylcaprolactam, etc.
• solvents of the formula (VI) are dimethyl sulfoxide, diphenyl sulfone, sulfolane, etc.
• basic catalysts examples include basic (earth) alkali salts such as sodium hydroxide, potassium hydroxide, sodium ethanolate, potassium carbonate, potassium hydrogen carbonate, etc.
• the reaction mixture Before the reaction (condensation), the reaction mixture can preferably be dewatered azeotropically. For this, e.g. a common entrainer such as toluene, mesitylene, chlorobenzene, dichlorobenzene, etc. is added.
• the reaction is preferably carried out under inert gas (e.g. nitrogen, argon).
• inert gas e.g. nitrogen, argon
• the reaction temperature is gradually increased, preferably to 150 to 250 ° C., and water and entrainer are removed from the reaction mixture. A gradual increase in viscosity can be observed.
• the polymer is then isolated by precipitation, for example from alcohols or alcohol / water mixtures, for example methanol, ethanol or isopropanol.
• aromatic polyethers according to the invention are distinguished, inter alia, by the fact that their physicochemical properties can be varied chemically by reactions on the pendant substituted phenyl radicals Ph. For example, oxidation of a mercapto group to the sulfone is easily possible.
• the new aromatic polyethers are more hydrophilic than PPO.
• they are well suited for the production of membranes. These membranes can be used for gas separation etc.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Polyethers (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1988
  • 1988-11-15 DE DE3838644A patent/DE3838644A1/de not_active Withdrawn
• 1989
  • 1989-11-03 EP EP19890120320 patent/EP0369248A3/fr not_active Withdrawn
  • 1989-11-09 JP JP1290118A patent/JPH02182723A/ja active Pending
  • 1989-11-13 US US07/435,045 patent/US5004836A/en not_active Expired - Fee Related

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